CN113151854A - Multi-metal non-oxide electrocatalyst and preparation method and application thereof - Google Patents
Multi-metal non-oxide electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 166
- 239000006185 dispersion Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 49
- 229910017116 Fe—Mo Inorganic materials 0.000 claims abstract description 43
- 229910020598 Co Fe Inorganic materials 0.000 claims abstract description 19
- 229910002519 Co-Fe Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 150000003346 selenoethers Chemical class 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 125000003748 selenium group Chemical class *[Se]* 0.000 claims abstract 4
- 239000002244 precipitate Substances 0.000 claims description 78
- 239000007788 liquid Substances 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 29
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- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000000919 ceramic Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 229910004647 CaMoO4 Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
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- 238000005119 centrifugation Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000013171 zeolitic imidazolate framework-6 Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- 230000015572 biosynthetic process Effects 0.000 description 30
- 238000003786 synthesis reaction Methods 0.000 description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000002243 precursor Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 229910018162 SeO2 Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910015667 MoO4 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004098 selected area electron diffraction Methods 0.000 description 3
- 150000003342 selenium Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910015793 MoP2 Inorganic materials 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012938 design process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
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- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a multi-metal non-oxide electrocatalyst and a preparation method and application thereof, wherein a Co-Fe layered double hydroxide is prepared by a coprecipitation method under the protection of nitrogen by using a metal organic framework ZIF-6 and a ferrous salt; adding molybdate aqueous solution into alcohol dispersion of Co-Fe layered double hydroxide, and preparing Co-Fe-Mo layered double hydroxide by coprecipitation; finally, annealing the Co-Fe-Mo layered double hydroxide and the phosphate solid in a tube furnace under the protective atmosphere to obtain Co-Fe-Mo phosphide; and carrying out solvothermal reaction on the Co-Fe-Mo layered double hydroxide and the selenium salt solution to obtain the Co-Fe-Mo selenide. The preparation method of the electrocatalyst is simple and convenient to operate, low in cost and rich in raw material source, the prepared multi-metal non-oxide electrocatalyst is derived from a metal organic framework structure, and multi-metal atoms are synergistic with one another, so that the electrocatalytic activity of the electrocatalyst is effectively improved. When directly used as an electrocatalyst for oxygen evolution reaction, the catalyst shows smaller overpotential, lower Tafel slope and good cycling stability.
Description
Technical Field
The invention belongs to the technical field of preparation and application of catalysts, and relates to a multi-metal non-oxide electrocatalyst, and a preparation method and application thereof.
Background
The decrease in fossil fuel resources and the further exacerbation of global environmental problems, clean and renewable hydrogen energy has become the most ideal energy alternative. The electrolyzed water is passed through an Oxygen Evolution Reaction (OER) at the anode and a Hydrogen Evolution Reaction (HER) at the cathode to produce oxygen (O)2) And hydrogen (H)2) This process becomes one of the most desirable and promising methods for large-scale production of hydrogen. However, anode OER involves the transfer of four electrons and four protons, and from a thermodynamic point of view, the reaction proceeds with a greater resistance. At present, RuO2And IrO2The oxygen evolution electrocatalyst is an effective electrocatalyst for oxygen evolution reaction, but the cost is high, the storage capacity is low, and the large-scale commercial application of the electrocatalyst is seriously influenced, so the development of the oxygen evolution electrocatalyst with high activity, high durability, low price and rich storage capacity has important significance for overcoming the technical difficulty of water electrolysis.
In recent years, oxides based on transition metals (Co, Ni, Fe, Mo, etc.) and Layered Double Hydroxides (LDHs) have been found to exhibit superior OER performance, and particularly, iron-cobalt-based nanomaterials are widely used in devices for total hydrolysis. However, such catalysts tend to aggregate, resulting in limited effective electroactive sites themselves exposed, and thus still have very limited utility in reducing overpotentials and tafel slopes in OER processes. Therefore, the method obtains the cheap electrocatalyst with better superiority and higher stability, and has important significance for developing friendly water electrolysis technology.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a multi-metal non-oxide electrocatalyst, a preparation method and application thereof, the preparation method is simple and convenient to operate, low in cost, rich in raw material source and reasonable in design process, the obtained multi-metal non-oxide electrocatalyst has smaller over potential and lower Tafel slope, can be directly used as an oxygen evolution reaction electrocatalyst, shows good OER performance and cycle stability, and is expected to realize the application value.
In order to achieve the purpose, the invention provides the following technical scheme: a method of preparing a multi-metal non-oxide electrocatalyst, comprising the steps of:
s1, adding a molybdate aqueous solution into an alcohol dispersion liquid of the Co-Fe layered double hydroxide to obtain a first mixed solution, heating the first mixed solution, centrifuging, washing and drying to obtain the Co-Fe-Mo layered double hydroxide;
s2, respectively placing the Co-Fe-Mo layered double hydroxide and the phosphate solid in a porcelain boat, placing the porcelain boat in a tube furnace, annealing in a protective atmosphere, and cooling to obtain Co-Fe-Mo phosphide;
s3, mixing, reacting and centrifuging the Co-Fe-Mo layered double hydroxide and the selenium salt solution to obtain black precipitate, washing and drying to obtain the Co-Fe-Mo selenide.
Further, in step S1, the volume ratio of the alcohol dispersion liquid of the Co-Fe layered double hydroxide to the molybdate aqueous solution is (4-5): 1; the molybdate is Na2MoO4·2H2O or CaMoO4·4H2And O, the solid-to-liquid ratio of the molybdate to the deionized water in the molybdate aqueous solution is 1: (80-100).
Further, in step S1, the first mixed solution reacts at 80 to 85 ℃ for 15 to 20min, the precipitate obtained by centrifugation is washed with water, and the drying is vacuum drying at 65 to 70 ℃ for 10 to 12 h.
Further, in step S2, the mass ratio of the Co-Fe-Mo layered double hydroxide to the phosphate is 1 (10-20).
Further, in step S2, the porcelain boat containing the phosphate solid is placed on the upstream side of the tube furnace, and the porcelain boat containing the Co-Fe-Mo layered double hydroxide is placed on the downstream side of the tube furnace; the annealing temperature is 300-320 ℃, and the annealing time is 1.5-2 h.
Further, in step S3, the selenium salt solution is prepared from (3-3.5): SeO of (1-1.2)2Alcohol solution and N2H4·H2Mixing the selenium salt solution with Co-Fe-Mo layered double hydroxide, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene inner container with the filling degree of 60-80% under continuous magnetic stirring, and reacting for 10-12 h at 140-160 ℃; the drying adopts vacuum drying, the drying temperature is 60-75 ℃, and the drying time is 18-24 h.
Further, in step S1, the Co-Fe layered double hydroxide is prepared by mixing a ferrous salt aqueous solution and a ZIF-67 alcohol dispersion, stirring, centrifuging, washing, and drying; the ZIF-67 is formed by Co (NO) with the molar ratio of 1 (5-10)3)2·6H2O and 2-methylimidazole through mixing reaction.
Further, the ferrous salt is FeCl2·4H2O or FeSO4·6H2O, the solid-to-liquid ratio of the ferrous salt to the deionized water in the ferrous salt aqueous solution is 1: (25-30), wherein the solid-to-liquid ratio of the ZIF-67 to the alcoholic solution in the ZIF-67 alcoholic dispersion liquid is 1 (450-550); the washing adopts ethanol, and the drying is carried out for 10 to 12 hours at 65 to 70 ℃ under the vacuum condition.
The invention also provides the multi-metal non-oxide electrocatalyst prepared by the preparation method, and the current density is 10mA/cm2When the over-potential of the multi-metal non-oxide electrocatalyst is 273 mV-298 mV, the Tafel slope is 24mV dec-1～29mV·dec-1。
The invention also provides application of the multi-metal non-oxide electrocatalyst in electrocatalytic oxygen evolution reaction.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention discloses a preparation method of a multi-metal non-oxide electrocatalyst, which is characterized in that CoFeMo-LDH is prepared by molybdate aqueous solution and Co-Fe layered double hydroxide, and the CoFeMo-LDH is phosphorized or selenized to generate the electrocatalyst which is derived from a metal organic framework structure and has more active reaction sites, so that the contact probability of the electrocatalyst and electrolyte is increased, and the reaction rate is greatly improved; and a plurality of metals in the catalyst can generate a catalytic synergistic effect, so that the transfer process of electrons in the electrocatalytic reaction is accelerated, the rate of the oxygen precipitation reaction can be effectively improved, the preparation method is simple and controllable, the cost is low, the raw material source is rich, the design process is reasonable, the high-efficiency and stable oxygen evolution reaction electrocatalyst can be obtained, and the application value of the electrocatalyst is expected to be realized.
The high-efficiency oxygen evolution electrocatalytic material with the hierarchical porous structure has the advantages of large specific surface area, adjustable aperture, easy modification and the like, and the current density is 10mA/cm2The overpotential of the catalyst is 273 mV-298 mV, and the Tafel slope is 24mV dec-1～29mV·dec-1The catalyst has smaller over potential and lower Tafel slope, can be directly used as an electrocatalyst for oxygen evolution reaction, and shows good OER performance and cycle stability.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of Co-Fe-Mo phosphide (CoFeMo-P) obtained in example 1;
FIG. 2 is an X-ray diffraction (XRD) pattern of Co-Fe-Mo selenide (CoFeMo-Se) made in example 7;
FIG. 3 is an X-ray diffraction (XRD) pattern of CoFeMo-P obtained from example 1, example 3 and example 4;
FIG. 4 is a Scanning Electron Microscope (SEM) image of CoFeMo-P micro-nano particles prepared in example 1;
FIG. 5 is a Scanning Electron Microscope (SEM) image of CoFeMo-Se micro-nano particles prepared in example 7;
FIG. 6 is a CoFeMo-P Selected Area Electron Diffraction (SAED) plot obtained in example 1;
FIG. 7 is a LSV plot of CoFeMo-P made in examples 1, 3 and 4;
FIG. 8 is LSV diagram of CoFeMo-P and CoFeMo-Se micro-nano particles prepared in example 1 and example 7.
Detailed Description
The present invention is further described with reference to the following drawings and detailed description, the following examples do not limit the scope of the present invention, and any modification, improvement or equivalent replacement made within the principle of the present invention should be included in the protection scope of the present invention.
Example 1
firstly, 0.08g of ZIF-67 is dispersed in 40mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under an atmosphere, 20mL of ethanol and a solution containing 0.18g of FeCl2·4H2And quickly pouring 5mL of deionized water solution of O into the ZIF-67 alcohol dispersion liquid at room temperature, stirring for 30min, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and performing vacuum drying at 70 ℃ for 10h to obtain the CoFe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, 0.1g of Na is contained under stirring2MoO4·2H2And quickly pouring 10mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 85 ℃, and reacting for 15min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 10 hours in vacuum at 70 ℃ to obtain the CoFeMo-LDH.
Step 4, synthesis of Co-Fe-Mo non-oxide (CoFeMo-P):
0.03g of CoFeMo-LDH and 0.3g of NaH were mixed2PO2Putting the raw materials into porcelain boats respectively, introducing nitrogen into a tube furnace to fill NaH2PO2The ceramic boat is placed on the upstream side of the tube furnace, the ceramic boat filled with the CoFeMo-LDH is placed on the downstream side of the tube furnace, annealing is carried out for 2 hours at 300 ℃ in a nitrogen atmosphere, and then natural cooling is carried out to room temperature, so as to obtain the CoFeMo-P.
The particle size of the prepared CoFeMo-P is 0.4-0.6 μm according to SEM images, and the CoFeMo-P is measured by an electrochemical performance test of an electrochemical workstation: at a current density of 10mA/cm2An overpotential of 286mV, a Tafel slope of 28mV dec-1。
Example 2
firstly, 0.08g of ZIF-67 is dispersed in 36mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under an atmosphere, 20mL of ethanol and a solution containing 0.18g of FeCl2·4H2And 4.5mL of deionized water solution of O is quickly poured into the ZIF-67 alcohol dispersion liquid at room temperature, stirred for 30min, centrifuged to obtain precipitate, the precipitate is washed with ethanol for 3 times, and dried in vacuum at 65 ℃ for 12h to obtain the CoFe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, under stirring, the solution containing 0.1g of CaMoO4·4H2And quickly pouring 8mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 80 ℃, and reacting for 20min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 12 hours in vacuum at 65 ℃ to obtain the CoFeMo-LDH.
Step 4, synthesis of Co-Fe-Mo non-oxide (CoFeMo-P):
0.03g of CoFeMo-LDH and 0.4g of NaH were mixed2PO2Putting the raw materials into porcelain boats respectively, introducing nitrogen into a tube furnace to fill NaH2PO2The ceramic boat is placed on the upstream side of the tube furnace, the ceramic boat filled with the CoFeMo-LDH is placed on the downstream side of the tube furnace, annealing is carried out for 1.5h at 320 ℃ in a nitrogen atmosphere, and then natural cooling is carried out to room temperature, so as to obtain the CoFeMo-P.
The electrochemical performance of the CoFeMo-P prepared by the method is measured by an electrochemical workstation: at a current density of 10mA/cm2The overpotential is 281mV, and the Tafel slope is 26mV dec-1。
Example 3
firstly, 0.08g of ZIF-67 is dispersed in 42mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under the atmosphere, 20mL of ethanol and a mixture containing 0.18g of FeSO4·6H2And quickly pouring 5mL of deionized water solution of O into the ZIF-67 alcohol dispersion liquid at room temperature, stirring for 30min, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and vacuum-drying at 70 ℃ for 12h to obtain the CoFe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, 0.1g of Na is contained under stirring2MoO4·2H2And (3) quickly pouring 9mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 83 ℃, and reacting for 18min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 10 hours in vacuum at 68 ℃ to obtain the CoFeMo-LDH.
Step 4, synthesis of Co-Fe-Mo non-oxide (CoFeMo-P):
0.03g of CoFeMo-LDH and 0.45g of NaH were mixed2PO2Putting the raw materials into porcelain boats respectively, introducing nitrogen into a tube furnace to fill NaH2PO2The ceramic boat is placed on the upstream side of the tube furnace, the ceramic boat filled with the CoFeMo-LDH is placed on the downstream side of the tube furnace, annealing is carried out for 1.8h at 310 ℃ in a nitrogen atmosphere, and then natural cooling is carried out to room temperature, so as to obtain the CoFeMo-P.
The electrochemical performance of CoFeMo-P was determined by electrochemical workstation: at a current density of 10mA/cm2When the voltage is high, the overpotential of CoFeMo-P is 273mV, and the Tafel slope is 24mV dec-1。
Example 4
firstly, 0.08g of ZIF-67 is dispersed in 44mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under an atmosphere, 20mL of ethanol and a solution containing 0.18g of FeCl2·4H2And quickly pouring 5.4mL of deionized water solution of O into the ZIF-67 alcohol dispersion liquid at room temperature, stirring for 30min, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and vacuum-drying at 70 ℃ for 10h to obtain the CoFe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, 0.1g of Na is contained under stirring2MoO4·2H2O in 8mL deionized WaterAdding the mixture into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 85 ℃, and reacting for 15min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 10 hours in vacuum at 70 ℃ to obtain the CoFeMo-LDH.
Step 4, synthesis of Co-Fe-Mo non-oxide (CoFeMo-P):
0.03g of CoFeMo-LDH and 0.6g of NaH were mixed2PO2Putting the raw materials into porcelain boats respectively, introducing nitrogen into a tube furnace to fill NaH2PO2The ceramic boat is placed on the upstream side of the tube furnace, the ceramic boat filled with the CoFeMo-LDH is placed on the downstream side of the tube furnace, annealing is carried out for 2 hours at 300 ℃ in a nitrogen atmosphere, and then natural cooling is carried out to room temperature, so as to obtain the CoFeMo-P.
The electrochemical performance of the CoFeMo-P prepared by the method is measured by an electrochemical workstation: at a current density of 10mA/cm2The time overpotential is 276mV, and the Tafel slope is 25mV dec-1。
Example 5
firstly, 0.08g of ZIF-67 is dispersed in 36mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under an atmosphere, 20mL of ethanol and a solution containing 0.18g of FeCl2·4H2And 4.5mL of deionized water solution of O is quickly poured into the ZIF-67 alcohol dispersion liquid at room temperature, stirred for 30min, centrifuged to obtain precipitate, the precipitate is washed with ethanol for 3 times, and dried in vacuum at 65 ℃ for 12h to obtain the CoFe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, under stirring, the solution containing 0.1g of CaMoO4·4H2And quickly pouring 8mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 80 ℃, and reacting for 20min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 12 hours in vacuum at 65 ℃ to obtain the CoFeMo-LDH.
Step 4, synthesis of Co-Fe-Mo non-oxide (CoFeMo-P):
0.03g of CoFeMo-LDH and 0.4g of Na were added3PO4Putting the raw materials into porcelain boats respectively, introducing nitrogen into a tube furnace to fill NaH2PO2The ceramic boat is placed on the upstream side of the tube furnace, the ceramic boat filled with the CoFeMo-LDH is placed on the downstream side of the tube furnace, annealing is carried out for 1.5h at 320 ℃ in a nitrogen atmosphere, and then natural cooling is carried out to room temperature, so as to obtain the CoFeMo-P.
The electrochemical performance of the CoFeMo-P prepared by the method is measured by an electrochemical workstation: at a current density of 10mA/cm2The overpotential is 281mV, and the Tafel slope is 26mV dec-1。
Example 6
firstly, 0.08g of ZIF-67 is dispersed in 36mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under an atmosphere, 20mL of ethanol and a solution containing 0.18g of FeCl2·4H2And 4.5mL of deionized water solution of O is quickly poured into the ZIF-67 alcohol dispersion liquid at room temperature, stirred for 30min, centrifuged to obtain precipitate, the precipitate is washed with ethanol for 3 times, and dried in vacuum at 65 ℃ for 12h to obtain the CoFe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, under stirring, the solution containing 0.1g of CaMoO4·4H2And quickly pouring 8mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 80 ℃, and reacting for 20min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 12 hours in vacuum at 65 ℃ to obtain the CoFeMo-LDH.
Step 4, synthesis of Co-Fe-Mo non-oxide (CoFeMo-P):
0.03g of CoFeMo-LDH and 0.5g of NaH were mixed2PO4Putting the raw materials into porcelain boats respectively, introducing nitrogen into a tube furnace to fill NaH2PO2The ceramic boat is placed on the upstream side of the tube furnace, the ceramic boat filled with the CoFeMo-LDH is placed on the downstream side of the tube furnace, annealing is carried out for 1.5h at 320 ℃ in a nitrogen atmosphere, and then natural cooling is carried out to room temperature, so as to obtain the CoFeMo-P.
The electrochemical performance of the CoFeMo-P prepared by the method is measured by an electrochemical workstation: at a current density of 10mA/cm2The overpotential is 281mV, and the Tafel slope is 26mV dec-1。
Example 7
firstly, 0.078g of ZIF-67 is dispersed in 38mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under the atmosphere, 25mL of ethanol and a solution containing 0.182g of FeSO4·6H2Rapidly pouring 5mL of deionized water solution of O into the ZIF-67 alcohol dispersion at room temperature, stirring for 30min, centrifuging to obtain precipitate,washing the precipitate with ethanol for 3 times, and vacuum drying at 70 deg.C for 12h to obtain Co-Fe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, under stirring, the solution containing 0.1g of CaMoO4·4H2And quickly pouring 10mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 85 ℃, and reacting for 15min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 10 hours in vacuum at 70 ℃ to obtain the CoFeMo-LDH layered double hydroxide.
Step 4, synthesis of Co-Fe-Mo selenide (CoFeMo-Se):
1mmol of SeO2Dissolved in 30mL of ethylene glycol, 10mL of N was added2H4·H2And O, obtaining a mixed solution.
Then adding 0.076g of CoFeMo-LDH into the mixed solution under the condition of continuous magnetic stirring, and stirring for 30 min; the resulting solution was then transferred to a polytetrafluoroethylene lined stainless steel autoclave with a 60% filling level and held at 140 ℃ for 10h to give a black precipitate.
And finally, centrifuging the black precipitate, washing the black precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the black precipitate for 24 hours in vacuum at the temperature of 60 ℃ to obtain CoFeMo-Se, wherein the grain diameter can be known to be 0.5-0.8 mu m through an SEM picture, and the electrochemical performance of the CoFeMo-Se is tested as follows: at a current density of 10mA/cm2The time overpotential is 293mV, and the Tafel slope is 26mV dec-1。
Example 8
firstly, 0.078g of ZIF-67 is dispersed in 38mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under the atmosphere, 25mL of ethanol and a solution containing 0.182g of FeSO4·6H2And rapidly pouring 5mL of deionized water solution of O into the ZIF-67 alcohol dispersion liquid at room temperature, stirring for 30min, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and vacuum-drying at 70 ℃ for 12h to obtain Co-Fe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, under stirring, the solution containing 0.1g of CaMoO4·4H2And quickly pouring 10mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 85 ℃, and reacting for 15min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 10 hours in vacuum at 70 ℃ to obtain the CoFeMo-LDH layered double hydroxide.
Step 4, synthesis of Co-Fe-Mo selenide (CoFeMo-Se):
1mmol of SeO2Dissolved in 30mL of ethylene glycol, 12mL of N was added2H4·H2And O, obtaining a mixed solution.
Then adding 0.077g of CoFeMo-LDH into the mixed solution under the condition of continuous magnetic stirring, and stirring for 30 min; the resulting solution was then transferred to a polytetrafluoroethylene-lined stainless steel autoclave with a filling degree of 70% and held at 150 ℃ for 11h, resulting in a black precipitate.
And finally, centrifuging the black precipitate, washing the black precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the black precipitate for 20 hours in vacuum at 70 ℃ to obtain CoFeMo-Se, wherein the electrochemical performance test of the CoFeMo-Se comprises the following steps: at a current density of 10mA/cm2The time overpotential is 295mV, and the Tafel slope is 28mV dec-1。
Example 9
firstly, 0.078g of ZIF-67 is dispersed in 38mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under the atmosphere, 25mL of ethanol and a solution containing 0.182g of FeSO4·6H2And rapidly pouring 5mL of deionized water solution of O into the ZIF-67 alcohol dispersion liquid at room temperature, stirring for 30min, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and vacuum-drying at 70 ℃ for 12h to obtain Co-Fe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, under stirring, the solution containing 0.1g of CaMoO4·4H2And quickly pouring 10mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 85 ℃, and reacting for 15min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 10 hours in vacuum at 70 ℃ to obtain the CoFeMo-LDH layered double hydroxide.
Step 4, synthesis of Co-Fe-Mo selenide (CoFeMo-Se):
1mmol of SeO2Dissolved in 35mL of ethylene glycol, 12mL of N was added2H4·H2And O, obtaining a mixed solution.
Then adding 0.075g of CoFeMo-LDH into the mixed solution under the condition of continuous magnetic stirring, and stirring for 30 min; the resulting solution was then transferred to a polytetrafluoroethylene-lined stainless steel autoclave with a filling degree of 80% and held at 160 ℃ for 12h, resulting in a black precipitate.
Finally, centrifuging the black precipitate, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and vacuum drying at 75 ℃ for 18h to obtain CoFeMo-Se and electrochemical reaction of the CoFeMo-SeAnd (3) testing the chemical properties: at a current density of 10mA/cm2The time overpotential is 293mV, and the Tafel slope is 29mV dec-1。
Example 10
firstly, 0.078g of ZIF-67 is dispersed in 38mL of ethanol to obtain ZIF-67 alcohol dispersion liquid;
then in N2Under the atmosphere, 25mL of ethanol and a solution containing 0.182g of FeSO4·6H2And rapidly pouring 5mL of deionized water solution of O into the ZIF-67 alcohol dispersion liquid at room temperature, stirring for 30min, centrifuging to obtain a precipitate, washing the precipitate with ethanol for 3 times, and vacuum-drying at 70 ℃ for 12h to obtain Co-Fe-LDH.
0.08g of CoFe-LDH is dispersed in 40mL of ethanol to obtain dark yellow CoFe-LDH dispersion liquid;
then, under stirring, the solution containing 0.1g of CaMoO4·4H2And quickly pouring 10mL of deionized water solution of O into the dark yellow CoFe-LDH dispersion liquid to obtain a mixed liquid, heating the mixed liquid to 85 ℃, and reacting for 15min to obtain a precipitate.
And centrifuging and washing the precipitate for 3 times by using water, and drying the precipitate for 10 hours in vacuum at 70 ℃ to obtain the CoFeMo-LDH layered double hydroxide.
Step 4, synthesis of Co-Fe-Mo selenide (CoFeMo-Se):
1mmol of SeO2Dissolved in 35mL of ethylene glycol, 10mL of N was added2H4·H2And O, obtaining a mixed solution.
Then adding 0.074g of CoFeMo-LDH into the mixed solution under the condition of continuous magnetic stirring, and stirring for 30 min; the resulting solution was then transferred to a 75% filled stainless steel autoclave lined with polytetrafluoroethylene and held at 160 ℃ for 10h to give a black precipitate.
And finally, centrifuging the black precipitate, washing the black precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying the black precipitate for 20 hours in vacuum at the temperature of 75 ℃ to obtain CoFeMo-Se, wherein the electrochemical performance test of the CoFeMo-Se comprises the following steps: at a current density of 10mA/cm2The time overpotential is 296mV, the Tafel slope is 26mV dec-1。
As shown in fig. 1, the broad diffraction peak of the XRD pattern appears around 2 θ ═ 20 °, demonstrating the amorphous alloy structure of CoFeMo-P. Since CoP (PDF No.29-0497), FeP (PDF No.39-0809) and MoP2(PDF No.16-0499) have similar orthogonal structures, which are favorable for CoP, FeP and MoP2Compounding to form amorphous alloy.
As shown in FIG. 2, the XRD characteristic diffraction peak and CoSe of the selenization product CoFeMo-Se in example 72(PDF no.53-0449)and FeSe2The diffraction peaks of (PDF No.21-0432) are overlapped, and in addition, the characteristic diffraction peak of CoFeMo-Se is sharper, which indicates that CoFeMo-Se with a polycrystalline structure is successfully prepared.
As shown in FIG. 3, the XRD pattern shows that the CoFeMo-P with different mass ratios has XRD pattern, and the change of mass ratio has less influence on the crystal structure of CoFeMo-P.
FIG. 4 shows an SEM image of CoFeMo-P, and FIG. 5 shows an SEM image of CoFeMo-Se. CoFeMo-P and CoFeMo-Se have similar morphological characteristics. They are rough in surface and have a large number of pore structures formed by a number of loose particles interconnected. The porous structure can not only expose more active sites, but also accelerate the mass transfer rate, thereby improving the catalytic activity of the porous structure.
As shown in fig. 6, the SAED spectrum of CoFeMo-P exhibits a bright aperture, indicating the amorphous structure of phosphide. The amorphous structure can expose more defect atoms due to the characteristics of long-range disorder and short-range order, thereby increasing the number of active sites and improving the oxygen catalytic activity.
As shown in FIG. 7, LSV profiles of CoFeMo-P formed by CoFeMo-LDH and phosphate with different mass ratios. It can be seen that the overpotential of the resulting CoFeMo-P is lowest when CoFeMo-LDH and phosphate are phosphated at a mass ratio of 1: 15. Therefore, the appropriate amount of phosphorus atoms are introduced into the obtained trimetallic layered double hydroxide, so that the OER electrocatalytic performance of the material can be effectively improved.
As shown in fig. 8, which is an LSV diagram of the CoFeMo-P and CoFeMo-Se micro-nano particles prepared in examples 1 and 7, it can be seen that the phosphated and selenized material has more excellent catalytic activity compared with LDH and ZIF-67. For CoFeMo-P, the current density is 10mA/cm2The time overpotential is 273mV, and the Tafel slope is 24mV dec-1(ii) a For CoFeMo-Se, the current density is 10mA/cm2The time overpotential is 293mV, and the Tafel slope is 26mV dec-1. CoFeMo-P has relatively highest catalytic activity, which is probably due to the existence of phosphide amorphous structure, and is beneficial to exposing more effective active sites, thereby improving the catalytic activity.
Claims (10)
1. A method for preparing a multi-metal non-oxide electrocatalyst, comprising the steps of:
s1, adding a molybdate aqueous solution into an alcohol dispersion liquid of the Co-Fe layered double hydroxide to obtain a first mixed solution, heating the first mixed solution, centrifuging, washing and drying to obtain the Co-Fe-Mo layered double hydroxide;
s2, respectively placing the Co-Fe-Mo layered double hydroxide and the phosphate solid in a porcelain boat, placing the porcelain boat in a tube furnace, annealing in a protective atmosphere, and cooling to obtain Co-Fe-Mo phosphide;
s3, mixing, reacting and centrifuging the Co-Fe-Mo layered double hydroxide and the selenium salt solution to obtain black precipitate, washing and drying to obtain the Co-Fe-Mo selenide.
2. The method for preparing a multi-metal non-oxide electrocatalyst according to claim 1, wherein in step S1, the volume ratio of the alcohol dispersion of Co-Fe layered double hydroxide to the molybdate aqueous solution is (4-5): 1; the molybdate is Na2MoO4·2H2O or CaMoO4·4H2And O, the solid-to-liquid ratio of the molybdate to the deionized water in the molybdate aqueous solution is 1: (80-100).
3. The method of claim 1, wherein in step S1, the first mixture is reacted at 80-85 ℃ for 15-20 min, the precipitate obtained by centrifugation is washed with water, and the drying is performed under vacuum at 65-70 ℃ for 10-12 h.
4. The method for preparing the multi-metal non-oxide electrocatalyst according to claim 1, wherein in step S2, the mass ratio of the Co-Fe-Mo layered double hydroxide to the phosphate is 1 (10-20).
5. The method of claim 1, wherein in step S2, the ceramic boat containing phosphate solid is placed on the upstream side of the tube furnace, and the ceramic boat containing Co-Fe-Mo layered double hydroxide is placed on the downstream side of the tube furnace; the annealing temperature is 300-320 ℃, and the annealing time is 1.5-2 h.
6. The method of claim 1, wherein in step S3, the selenium salt solution is prepared from the following components in a volume ratio of (3-3.5): SeO of (1-1.2)2Alcohol solution and N2H4·H2Mixing the selenium salt solution with Co-Fe-Mo layered double hydroxide, transferring the mixture into a reaction kettle with the filling degree of 60-80% under continuous magnetic stirring, and reacting at 140-160 ℃ for 10-12 h; the drying adopts vacuum drying, the drying temperature is 60-75 ℃, and the drying time is 18-24 h.
7. The method of claim 1, wherein in step S1, the Co-Fe layered double hydroxide is prepared from ferrous salt waterMixing the solution and ZIF-67 alcohol dispersion solution, stirring, centrifuging, washing, and drying to obtain the final product; the ZIF-67 is formed by Co (NO) with the molar ratio of 1 (5-10)3)2·6H2O and 2-methylimidazole through mixing reaction.
8. The method of claim 7, wherein the ferrous salt is FeCl2·4H2O or FeSO4·6H2O, the solid-to-liquid ratio of the ferrous salt to the deionized water in the ferrous salt aqueous solution is 1: (25-30), wherein the solid-to-liquid ratio of the ZIF-67 to the alcoholic solution in the ZIF-67 alcoholic dispersion liquid is 1 (450-550); the washing adopts ethanol, and the drying is carried out for 10 to 12 hours at 65 to 70 ℃ under the vacuum condition.
9. The multi-metal non-oxide electrocatalyst according to any one of claims 1 to 8, prepared by a process for preparing a multi-metal non-oxide electrocatalyst, characterized in that it has a current density of 10mA/cm2When the over-potential of the multi-metal non-oxide electrocatalyst is 273 mV-298 mV, the Tafel slope is 24mV dec-1～29mV·dec-1。
10. Use of a multi-metal non-oxide electrocatalyst according to claim 9 in electrocatalytic oxygen evolution reactions.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502487A (en) * | 2021-08-05 | 2021-10-15 | 先进能源产业研究院(广州)有限公司 | Preparation method of high-activity bifunctional oxygen electrocatalyst |
| CN114686915A (en) * | 2022-03-30 | 2022-07-01 | 上海工程技术大学 | Cobalt-iron bimetallic phosphide nanosphere derived from metal organic framework and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923268A (en) * | 2015-06-08 | 2015-09-23 | 中国科学院长春应用化学研究所 | Self-support transition metal selenide catalyst as well as preparation method and application thereof |
| CN108439354A (en) * | 2018-03-23 | 2018-08-24 | 桂林电子科技大学 | A kind of preparation method of metal selenide nano-powder |
| CN108722452A (en) * | 2018-05-30 | 2018-11-02 | 中国科学技术大学 | A kind of difunctional metal phosphide catalyst, preparation method and its application |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN109967099A (en) * | 2019-03-11 | 2019-07-05 | 浙江大学 | A kind of Co with hollow nanostructures2P@C composite and its preparation method and application |
| US20190229344A1 (en) * | 2018-04-04 | 2019-07-25 | Zolfaghar Rezvani | Oxidation of water using layered double hydroxide catalysts |
| US20210025064A1 (en) * | 2019-07-22 | 2021-01-28 | King Fahd University Of Petroleum And Minerals | Transition metal phosphide supported on carbon nanosheets |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111716B (en) * | 2020-01-19 | 2022-10-18 | 西北师范大学 | Preparation and application of nickel-cobalt double-metal phosphide guided by MOF |
-
2021
- 2021-03-19 CN CN202110298111.5A patent/CN113151854B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923268A (en) * | 2015-06-08 | 2015-09-23 | 中国科学院长春应用化学研究所 | Self-support transition metal selenide catalyst as well as preparation method and application thereof |
| CN108439354A (en) * | 2018-03-23 | 2018-08-24 | 桂林电子科技大学 | A kind of preparation method of metal selenide nano-powder |
| US20190229344A1 (en) * | 2018-04-04 | 2019-07-25 | Zolfaghar Rezvani | Oxidation of water using layered double hydroxide catalysts |
| CN108722452A (en) * | 2018-05-30 | 2018-11-02 | 中国科学技术大学 | A kind of difunctional metal phosphide catalyst, preparation method and its application |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
| CN109967099A (en) * | 2019-03-11 | 2019-07-05 | 浙江大学 | A kind of Co with hollow nanostructures2P@C composite and its preparation method and application |
| US20210025064A1 (en) * | 2019-07-22 | 2021-01-28 | King Fahd University Of Petroleum And Minerals | Transition metal phosphide supported on carbon nanosheets |
Non-Patent Citations (4)
| Title |
|---|
| PING HAN ET AL.: "Hierarchical porous structured trimetallic non-oxides CoFeMo-A (A= P, Se) as electrocatalysts for oxygen evolution reaction", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 932, pages 1 - 11 * |
| YANGYANG DING ET AL.: "Controllable synthesis of CoFeMo layered double hydroxide nanoarrays for promoting the oxygen evolution reaction", 《DALTON TRANS.》, vol. 49, pages 15417 * |
| YU-JIA TANG ET AL.: "In situ oxidation transformation of trimetallic selenide to amorphous FeCo-oxyhydroxide by self- sacrificing MoSe 2 for efficient water oxidation", 《J. MATER. CHEM. A》, vol. 8, pages 7925 * |
| YUN WU ET AL.: "A Novel Trimetal Phosphide with Amorphous Porous Structure for the Enhanced Electrocatalysis of Oxygen Evolution Reaction", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》, vol. 168, pages 116510 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502487A (en) * | 2021-08-05 | 2021-10-15 | 先进能源产业研究院(广州)有限公司 | Preparation method of high-activity bifunctional oxygen electrocatalyst |
| CN114686915A (en) * | 2022-03-30 | 2022-07-01 | 上海工程技术大学 | Cobalt-iron bimetallic phosphide nanosphere derived from metal organic framework and preparation method and application thereof |
| CN114686915B (en) * | 2022-03-30 | 2023-09-05 | 上海工程技术大学 | Cobalt-iron bimetallic phosphide nanosphere derived from metal organic framework, and preparation method and application thereof |
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